KR20000068093A - skin tanning compositions and method - Google Patents

Abstract

A cosmetic composition capable of artificially burning the skin consisting of dihydroxyacetone and azoles in a cosmetic or pharmaceutically acceptable carrier. Also provided is a method of artificially tanning skin consisting of providing dihydroxyacetone and azoles to the skin.

Description

Skin tanning compositions and method

Many people have irritated skin skin exposed to sunlight. Others may tan the skin after exposure to sunlight and experiencing significant discomfort, such as burns and other possible side effects. Many people want to burn the skin quite a bit for cosmetic and other reasons, and want to burn the skin with substances that tan the skin without actually being exposed to the sun.

In other cases, people who have difficulty burning skin want to extend the life of naturally obtained tans without re-exposing to the sun. Skin tanning also wants to be done in weather conditions where the sun exposure is not essential to tanning.

However, it is impossible for people with very weak skin to be burned rather than tanned to get a natural tan from exposure to the sun. In addition, it is a trend to generally recognize the harmful effects when excessive exposure to sunlight.

It is known in the art that artificial tanning is possible by applying the skin tanning material on a suitable carrier or base to human skin. Known skin tanning compositions include hydroxyaldehydes such as dihydroxyacetone known as DHA (U.S. Patent Nos. 2,949,403 to Andreadis et al. And 5,232,688 to Ziegler et al.). Also known as skin tanning agents are 4- (hydroxymethyl) imidazole (US Pat. No. 5,252,322 to Stoner et al.); Imidazole and various imidazole derivatives such as pyridine N-oxide and derivatives thereof (US Pat. Nos. 4,293,542 to Lang et al. And 4,228,151 to Lang et al.).

US Pat. No. 2,949,403 describes a method of using DHA as a substance to burn human epithelium and oily and hydroalcoholic compositions. U.S. Patent 5,232,688 includes alpha-hydroxy substituted ketones or aldehydes, such as DHA, the skin itself tanned, polyacrylamide and pharmaceutically acceptable carriers. DHA is a white crystal, hygroscopic powder with the formula C ₃ H ₆ O ₃ . When applied topically, DHA covalently binds to the amino groups of the skin epithelial protein to produce a cosmetically acceptable "burned" color (L. Goldman et al., "Investigative Studies with the Skin Coloring Agent; Dihydroxyacetone and Glyoxal," The Journal of Investigative Dermatology, 35, 161 (1960), and Bobin et al., "Effects of Color Adjuvants on The Tanning Effect of Dihydroxyacetone," J. Soc. Cosm. Chem., 35, 265 (1984)).

Since 1960, several compositions using DHA as active ingredient have been reported (US Patent Nos. 4,708,865 to Turner, 5,229,104 to Sottery et al., And 5,318,774 to Alban et al.), Such as octyl dimethyl PABA. A composition comprising a sunscreen composition and dihydroxyacetone has been reported (eg, US Patent Nos. 3,177,120 to Black et al. And 4,424,154 to McShane).

In addition, DHA is formulated as an oil-in-water emulsion to make formulations containing up to 50% alcohol, which tends to dry the skin, or "clean bases found on the hands and face. "I can make it creamy.

One of the disadvantages associated with the use of DHA as a skin tanning material is that a sufficient time required to react DHA to the skin in order to obtain the desired skin tanning appearance is generally required to be quite long, from 2 to 24 hours. This is the removal of highly water-soluble DHA from the skin surface, which is incompletely burned, especially when activities such as washing, bathing, swimming and sweating are present before DHA has a chance to fully react with skin proteins and amino acids. A second disadvantage is that orange skin peeling may be created which is undesirable when using DHA on normal skin. In some cases, dyes such as cut powder, dogwood powder, walnut powder and the like have been used to overcome this undesirable peeling (US Patent No. 4,708,865 to Turner), however, the skin is The use of such materials in a burned composition can result in very dark colors that are not aesthetically pleasing to the consumer.

US Pat. No. 5,252,322 describes a skin tanning composition comprising various imidazole derivatives such as imidazole and 4- (hydroxymethyl) imidazole. U.S. Patent 5,252,322 also describes that such compositions have the function of stimulating the skin's natural processes to tan the skin. This patent also describes some limitations on the use of imidazole in skin tanning compositions, such as the solubility of such compounds in water-soluble or alcoholic environments, and the use of such compounds above certain concentrations. In some cases, it is likely to irritate the skin.

In addition, US Pat. No. 5,252,322 describes that the imidazole compound is noticeably darkened in the skin of a test animal when used for a long time and repeatedly, for example, when used daily for at least 5 consecutive days.

Thus, there is a clear need for compositions that burn skin that can give a natural feel to the skin in a safe, non-irritating manner without dyes. There is also a need to provide a cosmetic consumer with a skin tanning composition that can tan the skin in a faster and more effective manner.

It is an object of the present invention to provide a skin tanning composition capable of providing a natural feeling of tan to the skin in a safe, irritating, rapid and effective manner. It is also an object of the present invention to provide a method of tanning the skin with a natural feel in a safe, irritating, quick and effective manner.

These and other objects of the present invention can be obtained by combining an effective amount of DHA with one or more azoles as a skin tanning composition in a cosmetic composition. We believe that the present invention is the first attempt to combine DHA and azole in such skin tanning compositions.

The present invention provides a surprisingly unexpected discovery that a combination of DHA and azoles, provided simultaneously or continuously to the skin, provides a natural feeling of tanning to the skin in a much faster time (typically 30 minutes) than with DHA alone. It is based. In addition, when the azole is an imidazole, the surprisingly unexpected finding that the concentration of imidazole, which is essential for making such tans in the skin, will be significantly lower than the existing known concentrations required when imidazole is used as the only skin tanning agent. Is based on.

Summary of the Invention

According to the present invention, there is provided a skin tanning composition as follows,

(a) dihydroxyacetone,

(b) azoles having the structure

Wherein X is S, O or NR ¹ , and R ¹ to R ⁴ may be the same or different and include hydrogen; phenol; C ₁ -C ₆ alkyl unsubstituted or substituted with phenyl, hydroxy carboxy, benzyloxy, amino, halogen, carboxylic acid, sun phosphate or phosphate; Or -CH ₂ -CH (COOR ') NR "R"' wherein R ', R ", R'" can be the same or different, which is hydrogen or C ₁ -C ₄ alkyl;

(c) consists of a cosmetically or pharmaceutically acceptable carrier.

The present invention also relates to a method of artificially burning human skin by applying the following dihydroxyacetone and azole to the skin;

Wherein X is S, O or NR ¹ , and R ¹ to R ⁴ may be the same or different and include hydrogen; phenol; C ₁ -C ₆ alkyl unsubstituted or substituted with phenyl, hydroxy carboxy, benzyloxy, amino, halogen, carboxylic acid, sun phosphate or phosphate; Or -CH ₂ -CH (COOR ') NR "R"', wherein R ', R ", R'" can be the same or different, which is hydrogen or C ₁ -C ₄ alkyl.

The compositions of the present invention are chemically and physically stable and, when used on the skin, are irritating and cosmetically satisfactory. They can provide natural tans to the skin in a safe, fast and effective manner.

The present invention provides a cosmetic composition and method for artificially tanning skin. More specifically, the present invention provides a composition for tanning skin comprising dihydroxyacetone and azole in a cosmetic or pharmaceutically acceptable carrier and artificially tanned by applying dihydroxyacetone and azole to human skin. Relates to the way.

The composition of the present invention consists of about 1 to 20 wt%, preferably about 3 to about 5 wt% of dihydroxyacetone by weight of the total composition. The exact amount of dihydroxyacetone used depends on the degree of sooting desired, which can be readily determined by one skilled in the art. In general, the higher the concentration of dihydroxyacetone used in a particular composition, the darker the color of the final skin.

The composition of the present invention is composed of azoles having the following structure;

Wherein X is S, O or NR ¹ , and R ¹ to R ⁴ may be the same or different and include hydrogen; phenol; C ₁ -C ₆ alkyl unsubstituted or substituted with phenyl, hydroxy carboxy, benzyloxy, amino, halogen, carboxylic acid, sun phosphate or phosphate; Or -CH ₂ -CH (COOR ') NR "R"', wherein R ', R ", R'" can be the same or different, which is hydrogen or C ₁ -C ₄ alkyl. Suitably the azole is imidazole, wherein X is S, O, or NR ¹ , thiador, wherein X is S. Most preferably the azole is imidazole itself, wherein R ¹ , R ² , R ³ , R ⁴ are monosubstituted imidazoles such as hydrogen or histidine, wherein R ¹ , R ² , R ³ are hydrogen, R ⁴ is —CH ₂ —CH (COOH) NH ₂ or 5-phenylimidazole, wherein R ¹ , R ² , R ³ are hydrogen, and R ⁴ is phenyl.

In a suitable embodiment, the azole is present in the weight of the total composition in an amount of 1.5 to about 7.5 wt%, more preferably about 1.5 to about 2 wt%.

In addition, the composition of the present invention further consists of a cosmetic or pharmaceutically acceptable carrier. As used herein, "cosmetic or pharmaceutical acceptable" refers to substances that are not known to be harmful to humans. These substances are described in CTFA International Cosmetic Ingredient Dictionary 4th Edition, The Cosmetic, Toiletry, and Fragrance Association, Inc., Washington, D.C., 1991, as well as in Remington's Pharmaceutical Sciences, 18th Edition, A.R. See Greenaro Ed., Mack Publishing Co., Easton, Pa., 1990. Suitable cosmetic or pharmaceutical compositions consistent with the object of the present invention include solutions, in particular hydroxide alcoholic solutions; Suspensions; Emulsions, in particular oil / water emulsions most particularly nonionic oil / water emulsions; Such as but not limited to gels, mousses, aerosols, and the like. The particular form of carrier employed depends on the physical, aesthetic and pharmaceutical properties of the desired final pharmaceutical composition.

In a suitable embodiment of the invention, the composition further comprises an organic acid such as alpha-hydroxy acid such as citric acid or beta-hydroxy acid such as salicylic acid. Coupling such an acid to the composition increases its physical and chemical stability over time, especially if the acid is present in an amount sufficient to lower the pH of the composition to about 3-5. Without being bound by theory, this increase in stability is seen as a result of the physical bonds formed between the azoles and the organic acids in the composition. Suitably the organic acid is present at about 5 wt% by weight of the total composition.

In a suitable embodiment of the invention, the composition further comprises at least one antioxidant, which acts as a stabilizer against oxidative degradation of the composition. Particularly preferred antioxidants are green tea extracts.

The composition of the present invention further includes a colloidal mineral dispersion, in particular colloidal, including ions derived from elements such as sodium, calcium, titanium, rubidium, lanthanum, yttrium, vanadium, cerium, neodynium, etc. Dispersions. Without being bound by theory, these ions act to provide a catalytic platform for the reaction between dihydroxyacetone and azoles in the skin. In particular, the colloidal mineral dispersion containing the above-mentioned ions can be purchased from The Rockland Corporation (Tulsa, OK) sold under the Body Booster trademark, which is preferred.

Various other optional ingredients can be included in the compositions of the present invention, for example emulsifiers, stabilizers, preservatives, emollients, preservatives, pigments, dyes, wetting agents, humectants, propellants, sunscreens and cosmetic or medical conditions. And other types of materials that may be present, but are not limited to these. Typical examples of such ingredients are provided in, but not limited to, the following examples.

Optional ingredients include emulsifiers such as Peg-100 stearate, glyceryl monostearate, DEA cetyl phosphate, dimethicone copolyol, TEA stearate and the like; Polyols such as glycerin and polyethylene glycol; Hydrocarbons such as mineral oil and petroleum; Fatty acid esters such as myristyl lactate and capryl and parric triglycerides, silicones; Emollients or diluents such as natural oils and components thereof; Humidifiers such as wheat fat extract or ceramides; Preservatives such as methyl paraben, butyl paraben, propyl paraben and phenoxyethanol; And mixtures thereof.

In another suitable embodiment of the invention, the composition consists of one or more sunscreens. As used herein, "sunscreen" is any substance that can effectively protect UV light by absorbing or dispersing such radiation from the skin or effectively reflecting UV radiation having a wavelength of about 280 to 400 nm. .

Suitable sunscreens include inorganic sunscreens such as titanium dioxide and zinc oxide; Organic sunscreens such as 2-ethylhexyl p-methoxycinnamate and mixtures thereof.

As mentioned above, the present invention relates to a method of artificially tanning human skin consisting of providing the skin with azole and dihydroxyacetone having the following structure;

Wherein X is S, O or NR ¹ , and R ¹ to R ⁴ may be the same or different and include hydrogen; phenol; C ₁ -C ₆ alkyl unsubstituted or substituted with phenyl, hydroxy carboxy, benzyloxy, amino, halogen, carboxylic acid, sun phosphate or phosphate; Or -CH ₂ -CH (COOR ') NR "R"', wherein R ', R ", R'" can be the same or different, which is hydrogen or C ₁ -C ₄ alkyl.

In a first embodiment of the method of the invention, dihydroxyacetone and azole are provided simultaneously to the actual skin, which is carried out via conventional cosmetic and pharmaceutical carriers. In a second embodiment, dihydroxyacetone and azole are provided sequentially to the skin, which is via a separate cosmetic or pharmaceutical carrier. In a third embodiment, azole is first given before dihydroxyacetone is provided to the skin.

The following examples are intended to illustrate, but are not limited to, various embodiments of the present invention.

Example 1

In vitro skin burn study

A useful model of skin tanning in vivo has shown the reaction of skin tanning substances and amino acids in vitro (L. Goldman et al., "Investigative Studies with the Skin Coloring Agents Dihydroxyacetone and Glyoxal," The Journal of Investigative Dermatology, 35, 161 (1960). The ability to tan the skin in this model is associated with the production of brown chromagen (λ _max = 428 nm), which can be measured with a spectrophotometer.

1 mL amino acid solution containing 1.0% w / v glutamine, glycine, lysine or alanine in buffer (pH 7.4) and a mixture of 2.0% w / v dihydroxyacetone, imidazole or dihydroxyacetone and imidazole (each concentration Participate in a 1 ml reaction solution containing 2.0% w / v). The resulting test solution is placed at 37 ° C. overnight after each test solution is read for absorbance at 428 nm using a Hewlett Packard Model 8452A UV / VIS spectrophotometer.

Absorbance due to chromagen formation in each test solution, A _chrom , can be calculated using the following formula;

A _chrom = A _{aa + react-} [A _aa + A _react ]

Where A _aa-react refers to the absorbance of the test solution at 428 nm;

A _aa refers to the absorbance of the amino acid blank solution at 428 nm;

A _react refers to the absorbance of the reactant blank solution at 428 nm.

The results are summarized in the following table.

amino acid Reactant A _{aa + react} A _aa A _react A _chrom Glutamine DHA 0.240 0.068 0.070 0.102 Imidazole 0.172 0.068 0.055 0.049 DHA / Imid. ^One 2.785 0.068 0.174 2.538 Glycine DHA 0.314 0.109 0.070 0.135 Imidazole 0.154 0.109 0.055 0 DHA / Imid. ^One 5.000 0.109 0.174 4.717 Lee Sin DHA 0.628 0.077 0.070 0.481 Imidazole 0.223 0.077 0.055 0.091 DHA / Imid. ^One 4.060 0.077 0.174 3.890 Alanine DHA 0.174 0.075 0.070 0.029 Imidazole 0.164 0.075 0.055 0.034 DHA / Imid. ^One 2.890 0.075 0.174 2.641

1 in the table refers to absorbance values corrected by dilution.

As can be seen from Table 1, it can be seen that the skin soot between dihydroxyacetone and azole is significantly enhanced in the presence of imidazole. In particular, the production of brown chromagen in the presence of imidazole enhanced 8, 25, 35, 91 times the reaction between dihydroxyacetone and lysine, glutamine, glycine and alanine without imidazole, respectively.

Example 2

In vivo skin burn study

A total of seven female volunteers in their twenties and fifties were selected for clinical studies to evaluate skin burn response after successive treatment with imidazole and dihydroxyacetone. Volunteers are healthy individuals with no evidence of acute or chronic disease, including skin or ophthalmic problems. The test site is free of warts, birthmarks, dark spots, (sun) burns, tans, scars and active skin lesions.

Each volunteer's right arm was treated with 2 ml of a 1% w / v solution in 50% aqueous ethanol. The solution is allowed to absorb into the skin for 5 minutes. A 3% w / v dihydroxyacetone solution in 50% aqueous ethanol is provided at the same site. The left arm of each volunteer is treated with dihydroxyacetone only.

The Minolta Chromameter Model CR200 is used to measure skin color before and after treatment at both sites for 30 minutes, 1 hour, 2 hours, 5 hours and 24 hours. As compared to the reference color, and calculates the reduction in reflectance (△ L ^*), an increase in red color (a ^* △), the increase in yellow (△ b ^*) and the like. The change in total color (ΔE ^* ) is calculated by the following equation;

△ E ^* = [(△ L ^* ) ² + (△ a ^* ) ² + (△ b ^* ) ² ] ^½

The results are summarized in the following table.

time ΔE ^* (DHA treatment) ΔE ^* (imidazole + DHA treatment) 30 minutes 0.85 1.98 1 hours 1.16 1.69 2 hours 1.64 2.03 5 hours 2.67 4.19 24 hours 2.97 4.04

As can be seen from Table 1, when the skin is treated continuously with imidazole and dihydroxyacetone, the skin color becomes significantly darker than when treated only with dihydroxyacetone. This continuous treatment resulted in a natural and noticeable skin burn after only 30 minutes.

Example 3

Skin tanned composition

Component weight ratio

Phase 1

Cetyl Alcohol 4.0

Stearyl Alcohol1.0

Stearth-21.5

Stearth-210.5

Coco Caprylate / Caprate 4.0

C _12-15 Alcohol Benzoate 5.0

Laureth-1 2.0

Glyceryl Stearate 3.0

Glyceryl Stearate /

PEG Isostearate 1.0

Propylene Glycol Diffel Argonate3.0

Phenyl Trimethicone5.0

Octyl Palmitate 4.0

Octyl hydroxystearate2.0

Phase 2

Purified water15.0

Glycerin 3.0

Butylene Glycol5.0

Imidazole1.5

Phase 3

Purified water

Dihydroxyacetone 5.0

Imidazole Urea 0.5

process

The components of phase 1 and the components of phase 2 are combined in separate containers. Combined phase 1 is added to the combined phase 2 at 70 ° C under stirring and then the product is cooled with stirring at 30 ° C. The components of combined phase 3 are then added and the resulting final mixture is cooled to room temperature to form a nonionic oil / water emulsion.

While the invention has been described in particular embodiments, those skilled in the art will recognize that various changes and modifications are possible. Accordingly, the invention is limited only by the appended claims.

Claims (38)

In the composition to burn skin, (a) dihydroxyacetone, (b) azoles having the structure Wherein X is S, O or NR ¹ , and R ¹ to R ⁴ may be the same or different and include hydrogen; phenol; C ₁ -C ₆ alkyl unsubstituted or substituted with phenyl, hydroxy carboxy, benzyloxy, amino, halogen, carboxylic acid, sun phosphate or phosphate; Or -CH ₂ -CH (COOR ') NR "R"' wherein R ', R ", R'" can be the same or different, which is hydrogen or C ₁ -C ₄ alkyl; (c) a composition comprising a cosmetically or pharmaceutically acceptable carrier. The composition of claim 1, wherein the dihydroxyacetone is present in an amount from about 1 to about 20 wt% in the weight of the total composition. The composition of claim 2, wherein the dihydroxyacetone is present in an amount from about 3 to about 5 wt% in the weight of the total composition. The composition of claim 1, wherein the azole is present in the weight of the total composition in an amount of about 1.5 to about 7.5 wt%. 5. The composition of claim 4, wherein the azole is present in the weight of the total composition in an amount of about 1.5 to about 2 wt%. The composition of claim 1, wherein X is NR ₁ or S. 7. The composition of claim 6, wherein R ¹ , R ² , R ³ are hydrogen. 8. The composition of claim 7, wherein R ⁴ is hydrogen. 8. The composition of claim 7, wherein R ⁴ is CH ₂ -CH (COOH) NH ₂ . 8. The composition of claim 7, wherein R ⁴ is phenyl. The composition of claim 1, further comprising an organic acid. 12. The composition of claim 11, wherein the organic acid consists of alpha-hydroxy acid and beta-hydroxy acid. 12. The composition of claim 11, wherein the organic acid is selected from citric acid and salicylic acid. 12. The composition of claim 11, wherein the organic acid is included in the weight of the total composition in an amount sufficient to lower the pH of the composition to about 3 to about 5. The composition of claim 11, wherein the organic acid is present in an amount of about 5 wt% in the weight of the total composition. The composition of claim 1 further comprising an antioxidant. The composition of claim 16 wherein the antioxidant is green tea extract. The composition of claim 1 wherein the cosmetic or pharmaceutically acceptable carrier is a hydroalcoholic solution. The composition of claim 1 wherein the cosmetic or pharmaceutically acceptable carrier is an oil / water emulsion. 20. The composition of claim 19, wherein the emulsion is nonionic. The composition of claim 1 further comprising a colloidal mineral dispersion. 22. The composition of claim 21 comprising a colloidal dispersion comprising ions derived from elements such as sodium, calcium, titanium, rubidium, lanthanum, yttrium, vanadium, cerium, neodymium and the like. The composition of claim 1, further comprising a solar cell vehicle. In the composition to burn skin, (a) dihydroxyacetone is present in about 1.0 to about 20 wt% of the total composition, (b) about 1.5 to about 7.5 wt% of an azole having the structure Wherein X is S, O or NR ¹ , and R ¹ to R ⁴ may be the same or different and include hydrogen; phenol; C ₁ -C ₆ alkyl unsubstituted or substituted with phenyl, hydroxy carboxy, benzyloxy, amino, halogen, carboxylic acid, sun phosphate or phosphate; Or -CH ₂ -CH (COOR ') NR "R"' wherein R ', R ", R'" can be the same or different, which is hydrogen or C ₁ -C ₄ alkyl; (c) an organic acid included in the weight of the total composition in an amount sufficient to lower the pH of the composition to about 3 to about 5. (d) a composition comprising a cosmetically or pharmaceutically acceptable carrier. 25. The composition of claim 24, wherein X is NR ₁ or S. The composition of claim 25, wherein R ¹ , R ² , R ³ are hydrogen. 27. The composition of claim 26, wherein R ⁴ is hydrogen. 27. The composition of claim 26, wherein R ⁴ is CH ₂ -CH (COOH) NH ₂ . 27. The composition of claim 26, wherein R ⁴ is phenyl. The composition of claim 24 further comprising a colloidal mineral dispersion. 31. The composition of claim 30 comprising a colloidal dispersion comprising ions derived from elements such as sodium, calcium, titanium, rubidium, lanthanum, yttrium, vanadium, cerium, neodynium and the like. A method of artificially burning human skin, the method comprising the steps of providing dihydroxyacetone and an azole having the formula: Wherein X is S, O or NR ¹ , and R ¹ to R ⁴ may be the same or different and include hydrogen; phenol; C ₁ -C ₆ alkyl unsubstituted or substituted with phenyl, hydroxy carboxy, benzyloxy, amino, halogen, carboxylic acid, sun phosphate or phosphate; Or -CH ₂ -CH (COOR ') NR "R"', wherein R ', R ", R'" can be the same or different, which is hydrogen or C ₁ -C ₄ alkyl. 33. The method of claim 32, wherein dihydroxyacetone and azole are provided simultaneously to the skin. 33. The method of claim 32, wherein dihydroxyacetone and azole are provided sequentially to the skin. 35. The method of claim 34, wherein the azole is provided to the skin before dihydroxyacetone is provided to the skin. 33. The method of claim 32, wherein X is NR ₁ and R ¹ , R ² , R ³ are hydrogen. A method of artificially tanning skin of a human, characterized by providing the skin composition of claim 1 to the human skin. A method for artificially tanning skin of a human, characterized by providing the skin composition of claim 24 to the human skin.